CN115779895A - Perovskite type catalyst and preparation method and application thereof - Google Patents
Perovskite type catalyst and preparation method and application thereof Download PDFInfo
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- CN115779895A CN115779895A CN202211389471.7A CN202211389471A CN115779895A CN 115779895 A CN115779895 A CN 115779895A CN 202211389471 A CN202211389471 A CN 202211389471A CN 115779895 A CN115779895 A CN 115779895A
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- perovskite
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- titanate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 19
- 239000005977 Ethylene Substances 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000002955 isolation Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 22
- 239000002002 slurry Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229910002367 SrTiO Inorganic materials 0.000 description 6
- 239000012018 catalyst precursor Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- AMXBISSOONGENB-UHFFFAOYSA-N acetylene;ethene Chemical group C=C.C#C AMXBISSOONGENB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
Abstract
The invention provides a perovskite catalyst and a preparation method and application thereof, belonging to the field of selective hydrogenation. The invention constructs the perovskite catalyst by using a doping-precipitation strategy to realize the isolation of catalytic hydrogenation sites, namely the hydrogen is activated by dissociating the active metal, the acetylene is activated by the perovskite substrate, so that the adsorption energy of the ethylene is weakened, the hydrogen molecule activating capacity of the active metal can be maintained, the surface of the perovskite has abundant oxygen vacancies, the isolation of the hydrogenation sites is realized, namely the active metal can only activate H 2 Oxygen vacancies on the perovskite substrate can activate alkyne to realize double-site synergistic hydrogenation, so that the catalyst has excellent selectivity and activity in acetylene hydrogenation reaction, and ethyleneHigh selectivity, good catalytic activity and high space-time yield; the perovskite catalyst has a stable structure, is not easy to generate sintering and other phenomena in the reaction process to cause site loss, and has good operation stability.
Description
Technical Field
The invention relates to the technical field of selective hydrogenation, in particular to a perovskite type catalyst and a preparation method and application thereof.
Background
Ethylene is an important chemical basic raw material, and the yield of ethylene is an important mark for measuring the national petrochemical level. Ethylene produced by petroleum cracking often contains small amounts (0.5 to 2 mol%) of acetylene, which poisons the Ziegler-Natta catalyst used in the downstream polyethylene production process, and therefore it is necessary to reduce the acetylene content to below 5 ppm. The selective hydrogenation can hydrogenate the acetylene impurity into the target product ethylene, and has extremely high atom utilization rate, so the selective hydrogenation is widely used in the industrial production process. However, since ethylene in the reaction material can also be hydrogenated and the concentration of ethylene is much higher than that of acetylene, in order to prevent the waste of raw materials caused by the hydrogenation of ethylene, the acetylene selective hydrogenation catalyst is required to have high acetylene hydrogenation activity and selectivity. At present, a supported palladium-based catalyst is used, and the adsorption energy of palladium on ethylene is weakened by using a metal auxiliary agent modification method to improve the selectivity, but the activation capability of metal palladium on acetylene and hydrogen is also reduced, so that the catalytic activity is seriously reduced. Therefore, there is a challenge to develop an acetylene selective hydrogenation catalyst having both high ethylene selectivity and high hydrogenation activity.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. The perovskite catalyst provided by the invention has high ethylene selectivity and high hydrogenation activity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a perovskite type catalyst, which comprises a perovskite substrate and active metal doped in the perovskite substrate, wherein the content of the active metal in the perovskite type catalyst is 0.01-10 wt%, and the content of the perovskite substrate is 90-99.99 wt%.
Preferably, the active metal comprises one or more of Pd, pt, cu, ni, rh, ru and In.
Preferably, the perovskite substrate is a titanate.
Preferably, the perovskite substrate comprises one or more of magnesium titanate, calcium titanate, strontium titanate and barium titanate.
Preferably, the perovskite substrate is a mixture of magnesium titanate and strontium titanate, and the molar ratio of the magnesium titanate to the strontium titanate in the mixture is 0.95-1.1.
The invention also provides a preparation method of the perovskite catalyst in the technical scheme, which comprises the following steps:
mixing a perovskite precursor, an active metal precursor and a solvent to obtain a mixed solution;
carrying out hydrothermal reaction on the mixed solution to obtain a hydrothermal product;
and sequentially roasting and reducing the hydrothermal product to obtain the perovskite type catalyst.
Preferably, the temperature of the hydrothermal reaction is 100-240 ℃ and the time is 12-48 hours.
Preferably, the roasting temperature is 400-900 ℃ and the roasting time is 3-6 hours.
Preferably, the temperature of the reduction is 120-200 ℃ and the time is 0.5-2 hours.
The invention also provides the application of the perovskite catalyst in the technical scheme or the perovskite catalyst prepared by the preparation method in the technical scheme in the selective hydrogenation reaction of acetylene.
The invention provides a perovskite type catalyst, which comprises a perovskite substrate and active metal doped in the perovskite substrate, wherein the content of the active metal in the perovskite type catalyst is 0.01-10 wt%, and the content of the perovskite substrate is 90-99.99 wt%.
Compared with the prior art, the invention has the following beneficial effects:
the invention constructs the perovskite catalyst by using a doping-precipitation strategy to realize the isolation of catalytic hydrogenation sites, namely the active metal dissociates and activates hydrogen, the perovskite substrate activates acetylene, thereby weakening the adsorption energy of ethylene and simultaneously maintaining the active hydrogen molecular capability of the active metal, the active metal is doped in the perovskite substrate, namely the active metal is covered by an oxide, the surface of the perovskite has rich oxygen vacancies, and realizes the isolation of the hydrogenation sites, namely the active metal can only activate H 2 Oxygen vacancies on the perovskite substrate can activate alkyne to realize double-site synergistic hydrogenation, so that the catalyst is prepared in the presence of the catalystThe acetylene hydrogenation reaction has excellent selectivity and activity, high ethylene selectivity, good catalytic activity and high space-time yield; the perovskite catalyst has a stable structure, is not easy to generate phenomena such as sintering and the like in the reaction process to cause site loss, and has good operation stability.
The invention also provides a preparation method of the perovskite catalyst in the technical scheme, and the preparation method is simple and easy to implement.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a graph of acetylene conversion and ethylene selectivity over reaction time for a perovskite catalyst prepared in example 1 of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The invention provides a perovskite type catalyst, which comprises a perovskite substrate and active metal doped in the perovskite substrate, wherein the content of the active metal in the perovskite type catalyst is 0.01-10 wt%, and the content of the perovskite substrate is 90-99.99 wt%.
In the present invention, the active metal preferably includes one or more of Pd, pt, cu, ni, rh, ru and In.
In the present invention, the perovskite substrate is preferably a titanate.
In the present invention, the perovskite substrate preferably comprises magnesium titanate (MgTiO) 3 ) Calcium titanate (CaTiO) 3 ) Strontium titanate (SrTiO) 3 ) And barium titanate (BaTiO) 3 ) One or more of (a).
In the present invention, the perovskite substrate is preferably a mixture of magnesium titanate and strontium titanate, and the molar ratio of magnesium titanate and strontium titanate in the mixture is preferably 0.95 to 1.1.
In the present invention, the content of the active metal in the perovskite catalyst is preferably 0.01 to 0.1wt%.
The invention also provides a preparation method of the perovskite catalyst in the technical scheme, which comprises the following steps:
mixing a perovskite precursor, an active metal precursor and a solvent to obtain a mixed solution;
carrying out hydrothermal reaction on the mixed solution to obtain a hydrothermal product;
and sequentially roasting and reducing the hydrothermal product to obtain the perovskite type catalyst.
According to the invention, a perovskite precursor, an active metal precursor and a solvent are mixed to obtain a mixed solution.
In the present invention, the active metal precursor is preferably a salt of an active metal, and when the active metal is preferably palladium, the salt preferably includes one or more of palladium nitrate, palladium chloride, palladium acetylacetonate, palladium acetate, ammonium tetrachloropalladate, and sodium tetrachloropalladate.
In the present invention, the solvent preferably includes one or more of deionized water, absolute ethanol, methanol, glacial acetic acid, n-hexane, and toluene. The invention has no special limitation on the dosage of the solvent, and the raw materials can be uniformly mixed.
In the present invention, the perovskite precursor preferably comprises a titanium source, the titanium source preferably comprises any one or more of titanium tetrachloride, titanium acetylacetonate, isopropyl titanate and tetrabutyl titanate, the metal source preferably comprises one or more of metal nitrate, metal sulfate, metal carbonate, metal chloride and metal hydroxide, and the metal element in the metal source preferably comprises one or more of magnesium, calcium, strontium and barium.
Preferably, the titanium source and the solvent are mixed to obtain a first solution, the metal source and the solvent are mixed to obtain a second solution, and the first solution, the second solution and the active metal precursor are mixed to obtain the mixed solution.
The invention has no special limit on the dosage of the titanium source, the metal source and the active metal precursor, and can meet the content of the active metal and the perovskite substrate in the perovskite type catalyst.
In the present invention, the time for mixing the first solution, the second solution and the active metal precursor is preferably 20 to 60min.
After the mixed solution is obtained, the mixed solution is subjected to hydrothermal reaction to obtain a hydrothermal product.
In the present invention, the temperature of the hydrothermal reaction is preferably 100 to 240 ℃ and the time is preferably 12 to 48 hours.
In the present invention, the hydrothermal reaction is preferably carried out in a hydrothermal reactor.
After the hydrothermal reaction is finished, the invention preferably carries out solid-liquid separation, washing and drying on the obtained slurry in sequence to obtain the hydrothermal product.
In the present invention, the solid-liquid separation is preferably centrifugation.
In the present invention, the washing is preferably performed by alternately washing with deionized water and absolute ethanol in sequence, and the specific manner of the washing is not particularly limited in the present invention and may be performed in a manner well known to those skilled in the art.
In the present invention, the drying temperature is preferably 60 to 120 ℃ and the time is preferably 6 to 12 hours.
After obtaining the hydrothermal product, sequentially roasting and reducing the hydrothermal product to obtain the perovskite catalyst.
In the present invention, the temperature of the calcination is preferably 400 to 900 ℃ and the time is preferably 3 to 6 hours.
In the present invention, the calcination is preferably carried out in air.
In the present invention, the temperature of the reduction is preferably 120 to 200 ℃ and the time is preferably 0.5 to 2 hours.
In the present invention, the reduction is preferably performed in a hydrogen atmosphere.
After the reduction is completed, natural cooling to room temperature is preferably further included.
The invention also provides the application of the perovskite catalyst in the technical scheme or the perovskite catalyst prepared by the preparation method in the technical scheme in the selective acetylene hydrogenation reaction.
In the invention, the pressure of the selective hydrogenation reaction of acetylene is preferably 0.1-0.3 MPa, the temperature is preferably 50-120 ℃, and H is H 2 And C 2 H 2 Preferably 5 to 20:1,C 2 H 4 And C 2 H 2 Preferably 20 to 40:1, the volume space velocity of the reaction is preferably 20,000-40,000h -1 。
In the present invention, the perovskite catalyst is preferably fixed with quartz wool at the time of use.
To further illustrate the present invention, the perovskite-type catalyst provided by the present invention, and the preparation method and application thereof, are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The catalyst is doped in SrTiO 3 The Pd nano-particles in the substrate are prepared by the following steps: dissolving 1.42g of isopropyl titanate in 40mL of absolute ethyl alcohol to prepare a uniform solution, dissolving 0.79g of strontium chloride in 20mL of deionized water to prepare a uniform solution, mixing the two solutions, adding 0.15mg of palladium chloride in the process of continuous stirring, stirring the slurry for 30min, transferring the slurry into a hydrothermal kettle, and placing the hydrothermal kettle into an oven to keep the temperature at 200 ℃ for 24h. And (3) centrifuging the slurry after hydrothermal treatment, alternately washing the slurry for 3 times by using deionized water and absolute ethyl alcohol, drying the slurry at 60 ℃ for 8 hours, and roasting the dried sample in air at 400 ℃ for 3 hours to obtain a catalyst precursor. And reducing the catalyst precursor at 180 ℃ in a hydrogen atmosphere for 1h, and then cooling to room temperature to obtain the perovskite catalyst.
Example 2
The catalyst is doped in MgTiO 3 Pd nano in substrateThe preparation method of the granules comprises the following steps: dissolving 1.42g of isopropyl titanate in 40mL of absolute ethyl alcohol to prepare a uniform solution, dissolving 0.48g of magnesium chloride in 20mL of deionized water to prepare a uniform solution, mixing the two solutions, adding 0.15mg of palladium chloride in the process of continuous stirring, stirring the slurry for 30min, transferring the slurry into a hydrothermal kettle, and placing the hydrothermal kettle into an oven to keep the temperature at 200 ℃ for 24h. And (3) centrifuging the slurry after hydrothermal treatment, alternately washing the slurry for 3 times by using deionized water and absolute ethyl alcohol, drying the slurry at 60 ℃ for 8 hours, and roasting the dried sample in air at 400 ℃ for 3 hours to obtain a catalyst precursor. And reducing the catalyst precursor for 1h at 180 ℃ in a hydrogen atmosphere, and then cooling to room temperature to obtain the perovskite catalyst.
Example 3
The catalyst is doped in CaTiO 3 The Pd nano-particles in the substrate are prepared by the following steps: dissolving 1.42g of isopropyl titanate in 40mL of absolute ethyl alcohol to prepare a uniform solution, dissolving 0.56g of calcium chloride in 20mL of deionized water to prepare a uniform solution, mixing the two solutions, adding 0.15mg of palladium chloride in the process of continuous stirring, stirring the slurry for 30min, transferring the slurry into a hydrothermal kettle, and placing the hydrothermal kettle into an oven to keep the temperature at 200 ℃ for 24h. And (3) centrifuging the slurry after hydrothermal treatment, alternately washing the slurry for 3 times by using deionized water and absolute ethyl alcohol, drying the slurry at 60 ℃ for 8 hours, and roasting the dried sample in air at 400 ℃ for 3 hours to obtain a catalyst precursor. And reducing the catalyst precursor at 180 ℃ in a hydrogen atmosphere for 1h, and then cooling to room temperature to obtain the perovskite catalyst.
Comparative example 1
The catalyst is loaded on SrTiO 3 The surface Pd nano-particles are prepared by the following method: 1g of SrTiO 3 Putting the powder into 60mL deionized water, performing ultrasonic treatment for 30min, adding palladium chloride into the solution, stirring and evaporating the solution at 60 ℃, calcining at 400 ℃, and reducing at 180 ℃ under the hydrogen condition to obtain the supported Pd perovskite catalyst, wherein the mass fraction of Pd is 0.01%.
Comparative example 2
The catalyst is loaded on CaTiO 3 The surface Pd nano-particles are prepared by the following steps: 1g of CaTiO 3 The powder was placed in a 60mL tankAnd (2) adding palladium chloride into the solution by ultrasonic treatment for 30min in deionized water, stirring and evaporating the solution at 60 ℃, calcining at 400 ℃ and reducing at 180 ℃ under the condition of hydrogen to obtain the supported Pd perovskite catalyst, wherein the mass fraction of Pd is 0.01%.
Comparative example 3
The catalyst is loaded on MgTiO 3 The surface Pd nano-particles are prepared by the following steps: 1g of MgTiO 3 Putting the powder into deionized water and performing ultrasonic treatment for 30min, adding palladium chloride into the solution, stirring and evaporating the solution at 60 ℃, calcining at 400 ℃, and reducing at 180 ℃ under the hydrogen condition to obtain the supported Pd perovskite catalyst, wherein the mass fraction of Pd is controlled to be 0.01%.
Comparative example 4
The catalyst was a commercial palladium on carbon catalyst.
The catalysts of comparative examples 1 to 4 and examples 1 to 3 were used for acetylene hydrogenation, and the specific activity evaluation experimental procedures were as follows: testing the activity of the catalyst using a fixed bed reactor, weighing 20mg of catalyst and placing it in the constant temperature section of the reactor, fixing both ends of the catalyst with quartz wool, the composition of the reaction gas being 1vol% 2 H 2 、10vol％C 2 H 4 、20vol％H 2 And the balance of Ar, the total flow rate of the gas is 40mL/min, the volume space velocity is 38,000h -1 The reaction temperature was 100 ℃ and the reaction pressure was 110kPa.
As shown in table 1, it can be seen from table 1 that the selectivity of the perovskite catalyst in the example of the present invention is significantly improved compared to the comparative example, and under the condition that the raw material gas contains ethylene, the full conversion of acetylene impurity and the ethylene selectivity of 80% or more can be achieved.
TABLE 1 catalyst acetylene Selective hydrogenation Activity
| Catalyst composition | Conversion of acetylene | Ethylene selectivity | |
| Comparative example 1 | Pd/SrTiO 3 | 85％ | 77％ |
| Comparative example 2 | Pd/CaTiO 3 | 92％ | 45％ |
| Comparative example 3 | Pd/ |
100％ | 32％ |
| Comparative example 4 | Palladium on |
100％ | 21％ |
| Example 1 | Pd- |
100％ | 96％ |
| Example 2 | Pd- |
100％ | 87％ |
| Example 3 | Pd- |
100％ | 82％ |
The catalysts of comparative examples 1 to 3 were prepared by a simple impregnation-reduction method without forming a complex oxide of metal and perovskite substrate, the reduced active metal was simply perovskite-supported, the interaction between the reduced active metal and the perovskite substrate was weak, the active metal did not form an oxide coating, and the perovskite substrate did not have abundant oxygen vacancies, resulting in that the metal sites can adsorb activated acetylene and the target product ethylene, so that the ethylene was further hydrogenated, resulting in the generation of by-products, and the catalytic performance was lowered.
Fig. 1 is a curve of acetylene conversion rate and ethylene selectivity of the perovskite catalyst prepared in example 1 of the present invention with the progress of reaction time, and it can be seen that the perovskite catalyst prepared in the present invention has a stable structure, is not easy to sinter during the reaction process to cause site loss, and has good operation stability.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The perovskite type catalyst is characterized by comprising a perovskite substrate and active metal doped in the perovskite substrate, wherein the content of the active metal in the perovskite type catalyst is 0.01-10 wt%, and the content of the perovskite substrate is 90-99.99 wt%.
2. The perovskite catalyst of claim 1, wherein the active metal comprises one or more of Pd, pt, cu, ni, rh, ru and In.
3. The perovskite catalyst of claim 1, wherein the perovskite substrate is a titanate.
4. The perovskite catalyst of claim 1 or 3, wherein the perovskite substrate comprises one or more of magnesium titanate, calcium titanate, strontium titanate, and barium titanate.
5. The perovskite catalyst of claim 4, wherein the perovskite substrate is a mixture of the magnesium titanate and the strontium titanate, and wherein the molar ratio of the magnesium titanate and the strontium titanate in the mixture is from 0.95 to 1.1.
6. The process for producing the perovskite catalyst as claimed in any one of claims 1 to 5, characterized by comprising the steps of:
mixing a perovskite precursor, an active metal precursor and a solvent to obtain a mixed solution;
carrying out hydrothermal reaction on the mixed solution to obtain a hydrothermal product;
and roasting and reducing the hydrothermal product in sequence to obtain the perovskite catalyst.
7. The process for producing a perovskite catalyst according to claim 6, wherein the hydrothermal reaction is carried out at a temperature of 100 to 240 ℃ for 12 to 48 hours.
8. The process for preparing a perovskite catalyst as claimed in claim 6, wherein the calcination is carried out at a temperature of 400 to 900 ℃ for 3 to 6 hours.
9. The process for producing a perovskite catalyst according to claim 6, wherein the reduction is carried out at a temperature of 120 to 200 ℃ for 0.5 to 2 hours.
10. Use of a perovskite catalyst as defined in any one of claims 1 to 5 or prepared by the preparation process as defined in any one of claims 6 to 9 in selective hydrogenation of acetylene.
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